Process for improving the durability and quality of a hair set and new products for carrying out this process

ABSTRACT

1. A METHOD OF TREATING UNCONSTRAINED HAIR IN A HAIR TREATING PROCESS TO IMPROVE AND PROLONG ITS SETTING PROPERTIES WITHOUT IMPARTING ANY PERMANENT DEFORMATION TO THE SAME COMPRISING THE STEPS OF FIRST APPLYING TO THE UNCONSTRAINED HAIR AN EFFECTIVE AMOUNT OF A COMPOSITON CONTAINING, IN AQUEOUS MEDIA, A THIOL REDUCING AGENT SELECTED FROM THE GROUP CONSISTING OF THIOGLYCOLIC ACID, THIOGLYCEROLL, GLYCOL THIOGLYCOLATE, GLYCEROL THIOGLYCOLATE, GLYCOL THIOLACTATE, B-MERCAPTO-ETHANOL, N-CARBOXYMETHYLMERCAPTO-ACETAMIDE, THIOLACTIC ACID AND B-MERCAPTOPROPIONIC ACID AND AN OXIDATION AGENT SELECTED FROM THE GROUP CONSISTING OF THE DISULFIDES OF THE FOLLOWING THIOLS; THIOGLYCOLIC ACID, THIOGLYCEROL, GLYCOL THIOGLYCOLATE, GLYCEROL THIOLGLYCOLATE, GLYCOL THIOLACTATE, B-MERCAPTO-ETHANOL, N-CAROXYMETHYL-MERCAPTO-ACETATMIDE, THIOLACTIC ACID AND B-MERCAPTOPROPIONIC ACID, THE MOLAR RATIO OF THE OXIDIZING AGENT TO SAID REDUCING AGENT BEING AT LEAST 1.5:1 AND UP TO 20:1, WITH THE AMOUNT OF REDUCING AGENT IN THE COMPOSITION BEING ABOUT 0.01-0.5 MOLE PER LITER AND THE AMOUNT OF OXIDIZING AGENT BEING ABOUT 0.015-10 MOLE PER LITER, SAID COMPOSITION HAVING A PH OF ABOUT 9-10, ALLOWING THE COMPOSITION TO REMAIN IN CONTACT WITH THE UNCONSTRAINED HAIR FOR ABOUT 1 TO 15 MINUTES AND THEREAFTER RINSING AND DRYING THE HAIR.

United States Patent Int. Cl. A61k 7/00 U.S. Cl. 424-47 Claims ABSTRACTOF THE DISCLOSURE Compositions for treating hair to improve itsmechanical properties containing at least a 1.5 molar concentration ofthiol disulfide oxidizing agent to thiol reducing agent having analkaline pH.

One of the important operations in hairstyling is the setting of thehair.

This operation consists essentially of rolling hair previously dampenedwith water or an aqueous solution on rollers whose diameters varyaccording to the desired effect, but which are generally of about tomillimeters. Next the hair is dried and the rollers are removed. Thenthe coiffure is completed by combing it out.

It has long been known that styles resulting from simple sets,especially those in which the hair has been dampened with water only, donot last well and are highly sensitive to humidity.

To remedy these defects, water-alcohol or alcoholic solutions of naturalor synthetic resins or polymers are used in the setting operation,though the results are not always completely satisfactory.

The applicants have just discovered that it is possible to notablyimprove the durability and quality of a set by giving the hair achemical treatment while the hair is in its natural state, that iswithout using curling pins, rollers or any other device designed to givehair a particular shape. Sets carried out in the usual manner on hair sotreated yield noticeably better results than sets on untreated hair.

The object of the present invention is to provide a new process fortreating hair so that it may be more effectively set, this process beingessentially characterized by the fact that after the hair has first beenwashed, it is impregnated with an alkaline solution consisting of amixture of at least one reducing agent belonging to the thiol class andat least one oxidizing agent consisting of a thiol disulfide. Thiscomposition is left to act for a sufficient length of time, for example,from 1 to 15 minutes, then the hair is thoroughly rinsed.

Another object of the invention is to provide a new process for settinghair, this process being essentially characterized by the fact that thehair is first treated as described above, then set in the conventionalmanner using water or an aqueous or water-alcohol solution of a settingresin.

In one embodiment of the invention, the aforecited treatment is carriedout while shampooing the hair.

In accordance with the invention, the composition containing the mixtureof thiol and disulfide has a pH falling between about 9 and 10. The pHof the composition may be regulated using ammonia or any organic ormineral base which may be used in cosmetics such as monoethanolamine,diethanolamine, or morpholine.

In accordance with the invention, some of the thiols which may be usedto carry out this process are: thioglycolic acid, thioglycerol, glycolthioglycolate, glycerol thioglycolate, glycol thiolactate,S-mercaptoethanol, N- carboxymethyl mercaptoacetamide, thiolactic acid,[3- mercaptopropionic acid, although this list is in no Way exhaustive.

Among the disulfides which may be used to carry out the invention arethose which correspond to the above thiols.

The proportion of the molar concentration of the disulfide to that ofthe thiol may vary widely, though it may never be less than about 1.5.Generally the proportion may vary up to about 20, but it is usually ofthe order of 2.5 and 15.

For each thiol-disulfide mixture, it is desirable, remembering the abovedirections, to determine the disulfide/ thiol molar ratio which yieldsthe best results.

According to the invention, a thiol may be used with its correspondingdisulfide, but this is not essential. It is equally possible to usecompositions containing mixtures of several thiols and severaldisulfides.

The thiol concentration in the compositions used to carry out thisprocess according to the invention may vary widely, but it is usuallybetween 0.01 and 0.5 mol/liter.

The process according to the invention has several advantages.

First, the process according to the invention results in sets which holdlonger than conventional sets obtained using pure water or resinsolutions.

Moreover, the improvement in the holding quality of the sets obtainedusing the process according to the invention is noticeable not only inthe first set thereafter, but also in later sets which may be carriedout without again using the process according to the invention.

In addition, it is much simpler to use the process according to theinvention than it is to use the permanent setting techniques which areknown today. Since the composition according to the invention is appliedto hair which has not yet been rolled on curling pins or rollers, thecomposition, in the form of a lotion of a fluid cream, may simply bebrushed into the hair.

Finally, hair treated according to the invention is easier to manage andlends itself to a better coifIure.

Another object of the present invention is to provide the new industrialproduct consisting of a cosmetic composition for treating hair with aview to notably improving the quality of later sets. This composition isessentially characterized by the fact that it is alkaline and that itcontains a mixture of at least one reducing agent belonging to the thiolclass and at least one oxidizing agent consisting of a thiol disulfidecompound. This composition may also have the diverse particulars citedabove during the discussion of the process utilizing this composition.

The composition according to the invention may take the form of liquidsolutions, creams or gels. It may also be packaged in the form ofaerosols for use in the spray state or as a lasting. or temporary foam.the form of liquid solutions, creams or gels. It may also contain othercosmetic additives such as perfumes or dyes to make the composition moreversatile, or cationic products to make it easier to untangle the hairand apply the composition, or swelling agents such as urea to make iteasier for the composition to penetrate to the interior of the keratinicfiber, or sequestrant agents so that the composition may be stored for alonger time.

Another object of the present invention is to provide the new industrialproduct which consists of a composition for simultaneously washing hairand treating it so that it may be more effectively set later. This newcomposition is essentially characterized by the fact that it contains atleast one detergent which may be used as a shampoo and a mixture of atleast one reducing agent belonging to the thiol class and at least oneoxidizing agent consisting of a thiol disulfide compound.

Conforming to the invention, the process described above may thus becarried out by simultaneously washing the hair and pretreating it sothat it may be more effectively set later.

In accordance with the invention, the various types of compounds knownfor their use in shampoos may be used in the composition.

For example, noniouic shampoos such as those which contain ethyleneoxides in their molecules may be used.

In such nonionic shampoos, the solubility may also be the result of OHfunctions fixed on the lipophile chain. Sugar esters belong to thiscategory of shampoos.

Anionic shampoos such as lauryl sulfate or dodecyl benzene sulfonate orcationic shampoos such as quaternary arnmonias or salts of fatty aminesmay also be used.

Finally, ampholite or amphoteric shampoos may be used, these being theshampoos which carry both negative and positive charges, as is the casefor example with the long-chain amino acids.

These compositions may contain for example from 2 to 10% detergent andfrom 0.5 to 10% thiol compounds, and from 3 to 50% thiol disulfidecompounds.

Conforming to the invention, the composition just described may be usedas a weekly or monthly shampoo so as to keep the hair in condition toundergo sets which will last longer and will be of better quality.

In order that the invention may be better understood, several exampleswill now be given by way of illustration, though they are in no wayexhaustive.

EXAMPLE 1 At the moment of use, the following composition is prepared:

Thioglycolic acid g Dithioglycerol g 5.7 Ammonia, q.s.p. pH=9.5

Distilled water, q.s.p cc 100 The hair is washed in the usual manner anddried. Next enough of this lotion is applied to impregnate all the hair.The lotion is left for 15 minutes, then the hair is thoroughly rinsedand set without using other ingredients.

The hair is dried under a hood, unrolled, and combed out.

It is noted that the application of such a solution makes the haireasier to style and that the set holds notably longer than aconventional set carried out under the same conditions.

EXAMPLE 2 The following solution is prepared:

Thiolactic acid g 1 Dithiodilactic acid g 5 Monoethanolamine, q.s.p.pH=9.5

Perfume g 0.5 Distilled water, q.s.p. cc 100 4 EXAMPLE 3 The twofollowing solutions are prepared and packaged separately:

Part A fi-Mercaptopropionic acid g 3 Monoethanolamine, q.s.p. pH=9.6Water, q.s.p cc 10 Part B Dithiodiglycerol g 40 Distilled water, q.s.p.cc

At the moment of use, equal volumes of these two solutions are mixed. Itis applied to the hair in the usual manner and the hair is then set.

Very satisfactory results are obtained. The holding quality of thecoiffure is notably improved for 5 to 6 weeks.

EXAMPLE 4 The two following solutions are prepared and packagedseparately:

The pH of this part B is about 3.

When parts A and B are mixed at the moment of use, the resin Carbopol934 contained in part B is neutralized by the excess alkali in part A.The mixture gels and the result is a thick paste whose pH equals 9.5 andwhich is extremely easy to apply.

The gel thus obtained is applied to the hair in the usual manner andexcellent results are obtained both from the point of view of ease ofapplication due to the form of the product and of the holding quality ofthe set.

The high holding quality of the coitfure lasts from 2 to 3 weeks.

EXAMPLE 5 At the moment of use, a composition having the followingformula is prepared:

Thioglycerol g 1 Dithiodiglycerol g 20 Lauryl ammonia sulfate g 25-Monoethanolamine, q.s.p. pH=9.5

Water, q.s.p. cc 100 10 cm. of this composition are used for the firstwashing of natural hair, then the hair is rinsed and 10 cm. more of thiscomposition are applied.

The scalp is massaged for several moments while the composition is beingemulsified, then there is a 10 minute wait.

The hair is then rinsed and immediately set using, if desired, aconventional setting lotion which may consis of a water-alcohol resinsolution. 1

The hair is rolled on rollers and dried. Then the rollers are removedand the hair is combed out.

It is noted that the hair falls into place easily and that it is bothsupple and strong.

The set holds much longer than if it had been carried out without thepre-treatment according to the invention.

After a week the hair may be washed again with a conventional shampooand set. The holding quality of this set also will be notably improved.

Experiments have shown that the particular qualities of these sets holdtrue for all sets carried out for a month after the pre-treatmentaccording to the invention.

After this time another pre-treatment using the abovedescribed shampoois necessary.

EXAMPLE 6 At the moment of use, a composition having the followingformula is obtained:

Thioglycerol 0.4

Dithiodiglycerol g 1.3

Lauric sulfate neutralized with soda plus 2 molecules of ethylene oxideg 25 Monoethanolamine, q.s.p. pH=9.5

Water, q.s.p cc 100 This composition is used regularly in place of aconventional shampoo.

Sets obtained this way hold for up to about 10 days.

The results are excellent, whether the solution is applied to natural orto lightly sensitized hair.

EXAMPLE 7 A shampoo powder is made by preparing dry the followingmixture:

Laurie sulfate with 50% active matter, neutralized with soda g 3Potassium thioglycolate g 0.5 Powdered dithiodiglycerol g 5 Kaolin g 1Sodium carbonate q.s.p. pH=9.5

For an aerosol shampoo, the following mixture is first prepared:

Laurie sulfate neutralized with soda plus 2 molecules of ethylene oxideg 50 Diethanolamide of fatty acid of copra g 2 Dithiodiglycerol g 40Thioglycerol g 2 Monoethanolamine q.s.p. pH=9.5 Water, q.s.p. cc 100This mixture is packaged in an aerosol bomb with the followingcomposition:

The above-described liquid 69 Fluoric hydrocarbon sold under thetrademark Freon 12 CCI F B.Pt. (-21.6 F.) 3

Butane 3 To use this shampoo, 10 to 15 grams of it are sprayed ondampened hair in the usual manner.

Again a notable improvement in the quality of later sets is obtained.

It will of course be appreciated that the foregoing examples have beengiven purely by way of illustration and could be modified as to detailwithout thereby departing from the basic principles of the invention.

What is claimed is:

1. A method of treating unconstrained hair in a hair treating process toimprove and prolong its setting properties without imparting anypermanent deformation to the same comprising the steps of first applyingto the unconstrained hair an effective amount of a compositioncontaining, in aqueous media, a thiol reducing agent selected from thegroup consisting of thioglycolic acid, thioglycerol, glycolthioglycolate, glycerol thioglycolate, glycol thiolactate,B-mercapto-ethanol, N-carboxymethylmercapto-acetamide, thiolactic acidand ,B-mercaptopropionic acid and an oxidizing agent selected from thegroup consisting of the disulfides of the following thiols: thioglycolicacid, thioglycerol, glycol thioglycolate, glycerol thioglycolate, glycolthiolactate, fi-mercapto-ethanol, N-carboxymethyl-rnercapto-acetamide,thiolactic acid and B-mercaptopropionic acid, the molar ratio of theoxidizing agent to said reducing agent being at least 1.5 :1 and up to20:1, with the amount of reducing agent in the composition being about0.01-05 mole per liter and the amount of oxidizing agent being about0.015-10 mole per liter, said composition having a pH of about 9-10,allowing the composition to remain in contact with the unconstrainedhair for about 1 to 15 minutes and thereafter rinsing and drying thehair.

2. The method of claim 1, in which the composition containing thereducing agent and the oxidizing agent also contains 2 to 10% by weightof a shampoo detergent.

3. The method of claim 1 in which the hair is initially washed beforebeing impregnated with the composition containing the reducing agent andthe oxidizing agent.

4. The method of claim 1 in which the amount of reducing agent isbetween 0.5 and 10% and the amount of oxidizing agent between 3 and 50%by weight of said composition.

5. The method of claim 1, wherein the composition is sprayed on the hairwith a propellant to initially form a light transient foam.

References Cited UNITED STATES PATENTS 2,719,813 10/1955 Haefele (I)424-72 2,719,814 10/ 1955 Haefele (II) 42472 2,719,815 10/1955 Sanders424-72 3,103,468 9/1963 Shepard et al 424-47 X 3,144,391 8/1964 Goff424-47 X FOREIGN PATENTS 1,336,311 7/1963 France.

ALBERT T. MEYERS, Primary Examiner F. E. WADDELL, Assistant Examiner US.Cl. X.R. 424-72

1. A METHOD OF TREATING UNCONSTRAINED HAIR IN A HAIR TREATING PROCESS TOIMPROVE AND PROLONG ITS SETTING PROPERTIES WITHOUT IMPARTING ANYPERMANENT DEFORMATION TO THE SAME COMPRISING THE STEPS OF FIRST APPLYINGTO THE UNCONSTRAINED HAIR AN EFFECTIVE AMOUNT OF A COMPOSITONCONTAINING, IN AQUEOUS MEDIA, A THIOL REDUCING AGENT SELECTED FROM THEGROUP CONSISTING OF THIOGLYCOLIC ACID, THIOGLYCEROLL, GLYCOLTHIOGLYCOLATE, GLYCEROL THIOGLYCOLATE, GLYCOL THIOLACTATE,B-MERCAPTO-ETHANOL, N-CARBOXYMETHYLMERCAPTO-ACETAMIDE, THIOLACTIC ACIDAND B-MERCAPTOPROPIONIC ACID AND AN OXIDATION AGENT SELECTED FROM THEGROUP CONSISTING OF THE DISULFIDES OF THE FOLLOWING THIOLS; THIOGLYCOLICACID, THIOGLYCEROL, GLYCOL THIOGLYCOLATE, GLYCEROL THIOLGLYCOLATE,GLYCOL THIOLACTATE, B-MERCAPTO-ETHANOL,N-CAROXYMETHYL-MERCAPTO-ACETATMIDE, THIOLACTIC ACID ANDB-MERCAPTOPROPIONIC ACID, THE MOLAR RATIO OF THE OXIDIZING AGENT TO SAIDREDUCING AGENT BEING AT LEAST 1.5:1 AND UP TO 20:1, WITH THE AMOUNT OFREDUCING AGENT IN THE COMPOSITION BEING ABOUT 0.01-0.5 MOLE PER LITERAND THE AMOUNT OF OXIDIZING AGENT BEING ABOUT 0.015-10 MOLE PER LITER,SAID COMPOSITION HAVING A PH OF ABOUT 9-10, ALLOWING THE COMPOSITION TOREMAIN IN CONTACT WITH THE UNCONSTRAINED HAIR FOR ABOUT 1 TO 15 MINUTESAND THEREAFTER RINSING AND DRYING THE HAIR.